Method of low-temperature stratified chilled water storage

ABSTRACT

The lower-most temperature of the thermal mass in a chilled water stratified storage tank is lowered without reducing its density by the addition of sodium nitrite and sodium nitrate, alone or in combination, preserving thermal stratification so that both warm and chilled water may be stored in the tank, a benefit not previously obtained without the use of chemicals damaging to the environment. A solution of sodium nitrite and sodium nitrate lowers the freezing point of the cooling water to -13.2° C. (8.3° F.) yet still permits the chilled water to stratify in the storage tank.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation in part of our application, U.S. Ser.No. 08/260,561, filed Jun. 16, 1994 and entitled METHOD OFLOW-TEMPERATURE STRATIFIED CHILLED WATER STORAGE), now U.S. Pat. No.5,465,585.

BACKGROUND OF THE INVENTION

This invention relates generally to a method for thermal energy storageand, particularly, to a method for storing thermal energy usingstratified chilled water.

There are a number of air conditioning and process cooling applicationsin which it is necessary to provide a measure of additional coolingcapacity during peak cooling periods. It is also generally necessary toprovide for the rejection of heat during these peak cooling periods.These requirements can be met using thermal energy storage.

One application for thermal energy storage might be found in a districtcooling system for providing cooling for a large number of buildingsfrom a single source. It is known in such a district cooling system thatit is possible to utilize equipment that has less cooling capacity thanthe peak demand requires by using thermal energy storage. Morespecifically, the chilling equipment is operated at night during aminimal demand period and chilled water is stored in a large thermalstorage tank. Then, when the demand increases during the day the chilledwater is drawn off from the tank to improve the ability of the coolingequipment to provide the required cooling. As an example of the scale ofsuch a district cooling system it is possible to use cooling equipmentthat has a 6,000 ton capacity to meet a cooling requirement of 11,000tons by using a thermal storage tank holding around three milliongallons of water.

Generally, such a thermal storage tank is always full, so that as cooledwater is drawn off from the bottom of the tank the warmer water isreturned at the top. The range of temperatures in such a tank istypically from 5.5° C. (42° F.) to 15.55° C. (60° F.) and between thesetemperatures the respective specific gravities of water increasessteadily as the temperature drops resulting in gravity separation suchas there would be in a conventional hot water tank, for example. Suchthermal storage tanks usually have some sort of non-mixing inlet/outletsystem so that the cooled outlet water is not mixed with the warm inletwater. Thus, the thermal storage tank will typically have a layer ofchilled water at around 5.5° C. (42° F.) at the bottom with a layer ofwarm water of up to 15.55° C. (60° F.) on top of the chilled water.

Further economic savings and other advantages could be achieved if thetemperature of the chilled water could be reduced without decreasing itsdensity. A storage and pipeline system could double its capacity usingthe same volume of water and the system would be able to serve newerbuildings which have 1.11° C. (34° F.) air conditioning systems. This isnot possible in a system employing only water as the thermal mass sink,because the maximum density of water occurs at 4.0° C. (39.2° F.). Attemperatures below 4.0° C. (39.2° F.) the density starts to decrease sothe cooler water will rise and stratified chilled water cannot bemaintained because the water mixes and the stratification is destroyed.

One common approach to increasing the ability of the thermal mass sinkto accept the rejected heat is to use chilled or refrigerated aqueoussolutions of brines, such as calcium chloride, sodium chloride, orglycol, all of which are capable of operating at temperatures below thefreezing point of water, 0° C. (32° F.). While these brine solutions orglycol solutions have been used for many years, they each haveparticular problems which require either expensive or presentlyunacceptable remedies. For example, brine solutions are corrosive andrequire the use of a corrosion inhibitor. The most commonly usedcorrosion inhibitor has been sodium chromate. Today, however, sodiumchromate is an environmentally unacceptable chemical and is, therefore,not available for use. On the other hand, industrial ethylene glycolsolutions are normally used in the range of 25% and in addition to theprohibitive cost in installations of the size mentioned above alsorequire inhibitors to control corrosion and chemical decomposition.Furthermore, microbiological decomposition of ethylene glycol can occurat solution concentrations below 20%, so that the higher solutionconcentrations must be used.

OBJECTS AND SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide amethod for storing stratified chilled water that can eliminate theabove-noted defects inherent in the previously proposed chemicaltreatments for thermal energy storage systems and that can provideincreased storage capacity.

Another object of this invention is to provide a method oflow-temperature stratified chilled water storage in which the freezingpoint of the water is depressed without destroying the ability toachieve stratification of the different temperature liquids in thethermal storage tank.

There is a further object of the present invention to provide aneconomically sized, depressed freezing point stratified chilled watersystem in which chemical solutions are used that are environmentallyacceptable and that do not require large amounts of expensive corrosioninhibitors.

In accordance with an aspect of the present invention, a method ofachieving low-temperature stratified chilled water storage involvesadding aqueous solutions of sodium nitrite and sodium nitrate separatelyor in combination to the water forming the thermal mass sink beingreturned in the thermal storage tank. Utilizing sodium nitrite andsodium nitrate alone or in combination in accordance with the presentinvention depresses the solution freezing point and permits a straightline density temperature curve of the overall system, resulting instratified storage of the thermal mass at temperatures below 4.4° C.(40° F.) and, more specifically, 4.1° C. (39.4° F.).

Various nitrite/nitrate solution concentrations can be utilized inpracticing the present invention. For example, the solutionconcentrations can range from less than 3% up to 25% and still obtainthe thermal savings benefits while remaining economically advantageous.

The above and other objects, features, and advantages of the presentinvention will become apparent from the following detailed descriptionof illustrative embodiments thereof, to be read in conjunction with theaccompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram of an overall cooling system employing thermalenergy storage that can benefit by following the present inventivemethod;

FIG. 2 is an elevational view in partial cross section of a waterstorage tank used in the system of FIG. 1;

FIG. 3 is a graph showing a straight line temperature versus densitycurve for a 3% nitrite/nitrate solution provided in accordance with anembodiment of the present invention;

FIG. 4 is a graph showing a straight line temperature versus densitycurve for a 7% nitrite/nitrate solution provided in accordance with anembodiment of the present invention;

FIG. 5 is a graph showing a straight line temperature versus densitycurve for a 15% nitrite/nitrate solution provided in accordance with anembodiment of the present invention; and

FIG. 6 is a graph showing a straight line temperature versus densitycurve for a 25% nitrite/nitrate solution provided in accordance with anembodiment of the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

FIG. 1 represents a typical application for air-conditioning or processcooling in which a cooling plant 10 provides the necessary chilled waterto a cooling distribution network 12 with the thermal storage beingprovided by a large water tank 14. The cooling plant 10 may relate to adistrict air-conditioning system or to a process cooling application andin both cases the thermal storage takes place in the water tank 14. Byproviding a means of increasing the chilling capacity of the thermalstorage without requiring more chilled water 14 it is possible toutilize a smaller capacity cooling plant 10 yet still provide all of thecooling required in the network 12 by operating more constantly overlonger periods of time and with higher efficiency during cooler hours.

FIG. 2 represents a typical water tank 20 used in a system such as thatof FIG. 1. In a large chilled-water cooling system this tank may be asbig as 127 feet in diameter and 90 feet high. It is in this large volumeof cooling liquid that the stratification must be maintained, so thatthe storage of both warm and chilled water in the same tank can beaccomplished.

As described above, such a storage tank 20 typically has a nonmixinginlet and outlet system to prevent agitation and mixing of the cooledwater and warm water as it is introduced into and drawn out of the tank.Such nonmixing can be accomplished using radial diffuser plates at theinlet/outlet at the top and bottom of the tank, shown respectively at 22and 24. Such nonmixing can also be accomplished using a two-pipe bafflesystem at each inlet and outlet. In such baffle system two pipes, notshown, are concentrically arranged with the apertures in the pipes beingoffset relative to each other.

Just as it is necessary to keep the cool water and warm water frommixing, it is also desirable to keep the interface thermocline no morethan 12 to 36 inches in thickness. The thermocline is the area of mixedtemperature water between the 5.5° C. (42° F.) chilled water and the15.55° C. (60° F.) return water. It will be understood that any mixing,as represented by a very thick thermocline layer, will reduce the amountof chilled water that can be stored at night for delivery to buildingsat the required temperature during the day. This interface layer or bandwill move up and down in the tank as chilled water is taken from oradded to the tank.

Maintaining this stratification is an important feature of the presentinvention and relates to the separation of liquids at differentdensities in a container when not exposed to turbulence or mixing due tofluid flow. The present invention teaches to take steps to change thedensity of the solution in proportion to the temperature change.Referring to FIG. 4, it is seen that the colder the solution, the higherthe density. For example, assume that the tank 20 is full of solution at12.22° C. (54° F.) with a density of 8.75 lbs/gal and chilled solutionis introduced through inlet diffuser 24 at -1.11° C. (30° F.) with adensity of 8.78 lbs/gal. The -1.11° C. (30° F.) solution will form alayer at the bottom of the tank 20 and will remain separatedindefinitely from the 12.22° C. (54° F.) solution, so long as there isno change in solution layer temperature. The above-described interfaceband or thermocline will exist between the two solution layers.

According to the present invention, the addition of sodium nitrite andsodium nitrate alone or in combination will permit stratified storage ofthe thermal mass below the 4.4° C. (40.0° F.) limit permitted whenutilizing water alone. In one embodiment, a 7% solution of sodiumnitrite and sodium nitrate in a 2 to 1 ratio is provided, however, thesolution concentration can range from below 3% to at least 25%. In threeother embodiments, 3%, 15% and 25% solutions of sodium nitrite andsodium nitrate in a 2 to 1 ratio are provided.

The use of the sodium nitrite/sodium nitrate solution permits storage ofthe chilled solution at lower temperatures than with only water. Forexample, the minimum temperature at which pure water can be stored in astratification mode is 3.88° C. (39° F.). At temperatures between 39° F.and the freezing point of 0° C. (32° F.) the density of water decreases,thus water colder than 3.88° C. (39° F.) will rise in the tank and thedesired stratification will not take place.

Although microbiological growth and degradation of sodium nitritefrequently occur in low level concentrations, the present inventionteaches that even when using concentrations for thermal storage of lessthan 5%, but not less than 3%, microbiological growth does not occur atthese concentrations and, in fact, the solution has been found to bemicrobicidal.

A further advantage in utilizing sodium nitrite to lower the temperatureof the chilled water is that sodium nitrite is readily oxidized tonitrate, either biologically or by chlorination. This means that suchnitrate can be removed from the waste water by natural biological actionor by aquatic vegetation.

The present invention teaches to depress the freezing point of thesolution to permit cooling below 0° C. (32° F.) and also to produce atemperature/density gradient to allow the production of a stratifiedthermal mass. FIG. 3 represents a straight line temperature/densitycurve attainable in keeping with the present invention by using a 3%sodium nitrite/sodium nitrate solution in a 2 to 1 ratio. FIG. 4represents a straight line temperature/density curve attainable inkeeping with the present invention by using a 7% sodium nitrite/sodiumnitrate solution in a 2 to 1 ratio. FIG. 5 represents a straight linetemperature/density curve attainable in keeping with the presentinvention by using a 15% sodium nitrite/sodium nitrate solution in a 2to 1 ratio. FIG. 6 represents a straight line temperature/density curveattainable in keeping with the present invention by using a 25% sodiumnitrite/nitrate solution in a 2 to 1 ratio.

Similar results are attainable using other salts of nitrite and nitrate,as well as salts of chloride and sulphates. Similarly, potassium andlithium nitrite/nitrate salts produce solutions with suitable physicalproperties with respect to lowering the freezing point and density,however, they are more expensive than the sodium salts.

A further advantage obtained by using sodium nitrite/sodium nitrateaccording to the present invention is the provision of corrosioninhibition for the metals employed in the cooling system. Althoughchloride and sulphate salts might be generally less expensive thansodium nitrite/sodium nitrate, they are corrosive and require theaddition of corrosion inhibitors. As a further problem with those othersalts, the most effective and only commercially available chloridecorrosion inhibitor is chromate, however, because of environmentalrestrictions chromate can not be used.

An example of the use of the above-described invention in theapplication of a commercially available product containing sodiumnitrite and sodium nitrate, in approximately a 2 to 1 ratio, in a largechilled water storage system is set forth below.

EXAMPLE 1--3%

The thermal storage operates at a chilled water temperature of -1.1° C.(30° F.) and in order to provide freeze protection in the system andequipment, a solution strength of 3% sodium nitrite and sodium nitratein a 2 to 1 ratio was prepared that has a freezing point of -1.6° (29.2°F.). This results in an approximate straight line temperature densitycurve over the system operating temperature range of -1.1° C. (30° F.)to 13.3° C. (56° F.). Tests relating to the use of a corrosion couponand the linear polarization resistance technique showed the 7% solutionwas not only non-corrosive to mild steel but also creates corrosioninhibitors, and is only moderately corrosive to copper and copperalloys. In this example, a 5.5 ppm of tolyltriazole was added and thissharply decreased the corrosion rate for copper and brass.

EXAMPLE 2--7%

The thermal storage operates at a chilled water temperature of -1.1° C.(30° F.) and in order to provide freeze protection in the system andequipment, a solution strength of 7% sodium nitrite and sodium nitratein a 2 to 1 ratio was prepared that has a freezing point of -3.75° C.(25.25° F.). This results in an approximate straight line temperaturedensity curve over the system operating temperature range of -1.1° C.(30° F.) to 13.3° C. (56° F.).

Tests relating to the use of a corrosion coupon and the linearpolarization resistance technique showed the 7% solution was not onlynon-corrosive to mild steel but also creates corrosion inhibitors, andis only moderately corrosive to copper and copper alloys. In thisexample, a 5.5 ppm of tolyltriazole was added and this sharply decreasedthe corrosion rate for copper and brass.

EXAMPLE 3--15%

The thermal storage operates at a chilled water temperature of -1.1° C.(30° F.) and in order to provide freeze protection in the system andequipment, a solution strength of 15% sodium nitrite and sodium nitratein a 2 to 1 ratio was prepared that has a freezing point of -7.5° C.(18.5° F.). This results in an approximate straight line temperaturedensity curve over the system operating temperature range of -1.1° C.(30° F.) to 13.3° C. (56° F.).

Tests relating to the use of a corrosion coupon and the linearpolarization resistance technique showed the 7% solution was not onlynon-corrosive to mild steel but also creates corrosion inhibitors, andis only moderately corrosive to copper and copper alloys. In thisexample, a 5.5 ppm of tolyltriazole was added and this sharply decreasedthe corrosion rate for copper and brass.

EXAMPLE 4--25%

The thermal storage operates at a chilled water temperature of -1.1° C.(30° F.) and in order to provide freeze protection in the system andequipment, a solution strength of 25% sodium nitrite and sodium nitratein a 2 to 1 ratio was prepared that has a freezing point of -13.2° C.(8.3° F.). This results in an approximate straight line temperaturedensity curve over the system operating temperature range of -1.1° C.(30° F.) to 13.3° C. (56° F.).

Tests relating to the use of a corrosion coupon and the linearpolarization resistance technique showed the 7% solution was not onlynon-corrosive to mild steel but also creates corrosion inhibitors, andis only moderately corrosive to copper and copper alloys. In thisexample, a 5.5 ppm of tolyltriazole was added and this sharply decreasedthe corrosion rate for copper and brass.

The solutions of the sodium nitrite and sodium nitrate mentioned abovewere tested for microbial activity using an inoculation procedure on thetest solution and a control sample of tap water. The results showed thatthe nitrite/nitrate solutions of 3% concentration or more are inhibitoryor microbicidal to microbiological growth. At concentrations of lessthan 3%, the nitrite/nitrate solutions are no longer microbicidal.

Further tests were made to determine the corrosion effect of thenitrite/nitrate solution at the air solution interface inside the steelthermal storage tank, such as represented in FIG. 2. The test resultsrevealed that corrosion at the interface and in the vapor phase isnegligible or nonexistent, thereby eliminating the requirement forprotective coatings.

It is understood of course that the foregoing is presented by way ofexample only and is not intended to limit the scope of the invention,which is to be defined solely by the appended claims.

What is claimed is:
 1. A method of low-temperature stratified chilledwater storage in a thermal storage tank, comprising steps of:preparing asodium nitrite and water solution; storing the prepared solution in astorage tank; chilling a portion of the stored, prepared solution to atemperature below 4.1° C. (39.4° F.); and introducing the chilledsolution at the bottom of the storage tank,whereby the tank contains alayer of the chilled solution at a temperature below 4.1° C. (39.4° F.)located below a layer of the prepared solution at a temperature above4.1 C. (39.4 F.).
 2. The method according to claim 1, wherein the stepof introducing includes preventing mixing between the chilled solutionbeing introduced and the solution already stored in the tank.
 3. Themethod according to claim 1, wherein the step of preparing includesadding 5.5 ppm of tolyltriazole.
 4. The method according to claim 1,wherein a 3%-25% solution of sodium nitrite and water is prepared. 5.The method according to claim 4, wherein the step of preparing includesadding 5.5 ppm tolyltriazole.
 6. A method of low-temperature stratifiedchilled water storage in a thermal storage tank, comprising stepsof:preparing a sodium nitrate and water solution; storing the preparedsolution in a storage tank; chilling a portion of the stored, preparedsolution to a temperature below 4.1° C. (39.4° F.); and introducing thechilled solution at the bottom of the storage tank,whereby the tankcontains a layer of the chilled solution at a temperature below 4.1° C.(39.4° F.) located below a layer of the prepared solution at atemperature above 4.1° C. (39.4° F.).
 7. The method according to claim6, wherein the step of introducing includes preventing mixing betweenthe chilled solution being introduced and the solution already stored inthe tank.
 8. The method according to claim 6, wherein a 3%-25% solutionof sodium nitrate and water is prepared.
 9. The method according toclaim 6, wherein the step of preparing includes adding 5.5 ppm oftolyltriazole.
 10. The method according to claim 8, wherein the step ofpreparing includes adding 5.5 ppm of tolyltriazole.
 11. A method oflow-temperature stratified chilled water storage in a thermal storagetank, comprising steps of:preparing a sodium nitrite, sodium nitrate andwater solution; storing the prepared solution in a storage tank;chilling a portion of the stored, prepared solution to a temperaturebelow 4.1° C. (39.4° F.); and introducing the chilled solution at thebottom of the storage tank, whereby the tank contains a layer of thechilled solution at a temperature below 4.1° C. (39.4° F.) located belowa layer of the prepared solution at a temperature above 4.1° C. (39.4°F.).
 12. The method according to claim 11, wherein the step ofintroducing includes preventing mixing between the chilled solutionbeing introduced and the solution already stored in the tank.
 13. Themethod according to claim 11, wherein the step of preparing includes thestep adding the sodium nitrite and sodium nitrate to the water in a 2 to1 ratio.
 14. The method according to claim 11, wherein the step ofpreparing includes adding 5.5 ppm of tolyltriazole.
 15. The methodaccording to claim 11, wherein a 3%-25% solution of sodium nitrite,sodium nitrate and water is prepared.
 16. The method according to claim15, wherein the step of preparing includes the step of adding the sodiumnitrite and sodium nitrate to the water in a 2:1 ratio.
 17. The methodaccording to claim 15, wherein the step of preparing includes adding 5.5ppm of tolyltriazole.
 18. The method according to claim 15, wherein thestep of introducing includes preventing mixing between the chilledsolution being introduced and the solution already stored in the tank.19. The method according to claim 15, wherein a 3% solution of sodiumnitrite, sodium nitrate and water is prepared.
 20. The method accordingto claim 15, wherein a 15% solution of sodium nitrite, sodium nitrateand water is prepared.
 21. The method according to claim 15, wherein a25% solution of sodium nitrite, sodium nitrate and water is prepared.